Hair dyeing compositions containing polyhydroxylated polyether nonionic surfactants

ABSTRACT

A composition for dyeing hair comprises an aqueous solution of a hair dye and a compound having the formula R1O - C2H3O(CH2OH-nH wherein the repeating group is linear, R is a lipophile group and n has a statistical average value greater than 1 and equal to or less than 10.

United States Patent Kalopissis et a1.

HAIR DYEING COMPOSITIONS CONTAINING POLYI-IYDROXYLATED POLYETHERNONIONIC SURFACTANTS Inventors: Gregoire Kalopissis, Paris; Guy

Vanlerberghe. Montjay-la-Tour, both of France Assignee: LOreal, Paris,France Filed: Oct. 4, 1971 Appl. No.: 186,524

Related US. Application Data Continuation-impart of Ser. No. 846,929,Aug. 1, 1969. Pat. No. 3,666,671, which is a continuation-in-part ofSer. No. 780,300, Nov. 29. 1968, Pat. No. 3.578.719, which is acontinuation-impart of Ser. No. 544,095, April 21. 1966. abandoned.

[ 1 Feb. 11,1975

[56] References Cited UNITED STATES PATENTS 1,402,317 1/1922 Rodehush260/636 2,089,569 8/1937 Orthner et 260/615 8 UX 2,131,142 9/1938Orthner et al.... 260/613 B UX 2.643.211 6/1953 DenBeslc r 8/101 X2.763.269 9/1956 DenBesle 8/1011 3.555.584 1/1971 Kalopissis et a1. 1.8/10.!

FOREIGN PATENTS OR APPLICATIONS 1.022,878 3/1966 Great Britain 260/613 BPrimary Examiner-Jerome D. Goldberg Assistant Examiner-Vera C. ClarkeAttorney. Agent, or Firm-Cushman, Darby 84 Cushman [57] ABSTRACT Acomposition for dyeing hair comprises an aqueous solution of a hair dyeand a compound having the formula R O C H:,O(CH OH 11;, H wherein therepeating group is linear, R is a lipophile group and n has astatistical average value greater than 1 and equal to or less than 10.

7 Claims. No Drawings 1 HAIR DYEING COMPOSITIONS CONTAININGPOLYHYDROXYLATED POLYETI-IER NONIONIC SURFACTANTS This application is acontinuation-in-part of our application SN 846,929, filed Aug, l, 1969,now U.S. Pat. No. 3,666,671, which is a continuation-in-part of ourapplication Ser. No. 780,300, filed Nov. 29, 1968, now US. Pat. No3,578,719, which in turn is a continuationin-part of our applicationSer. No. 544,095, filed Apr. 21, l966, now abandoned.

There are quite a number of known non-ionic surface active agents thecompositions and properties of which are quite varied.

Nevertheless the known products made from the conventional raw materialsdo not have simultaneously all the characteristics which are desired forcertain cos metic purposes.

For instance, the best detergents and foaming agents among thosemonoethers of polyethylene glycol which comprise a lipophile chainhaving at least 8 carbon atoms are generally the most irritating to themucous membranes. Moreover, when mixed with cationic surface activeagents the degree of irritation increases synergistically.

On the other hand, the derivatives ofthe polyols and the sugars,especially their esters, have been considered most useful because theyare not irritating. They have, however, certain disadvantages whichresult from their composition. In particular, the non'selectivecharacter of the reactions used in their preparation results in theformation of a mixture of constituents having one or more lipophilechains per molecule. When these products are to be used for applicationsfor which solubility in water is a prerequisite, they must therefore bepainstakingly purified.

The hydrosolubility of these compounds may be improved by addinghydrophile substituents on the carbon chain or by adding ethylene oxideto the free hydroxyl groups. However, such compounds are not usuallyvery good foaming agents, even when they comprise a medium lengthhydrocarbon chain. They are consequently used mainly as emulsifiers.

The object of the invention is to produce, from conventional commercialraw materials, new non-ionic surfaceactive agents which are stable, veryhydro philic, non-irritating, non-toxic and which may be used asemulsifiers, foaming agents, detergents, or wetting agents.

Another object of the present invention is to provide a method ofpreparing preferred new non-ionic surface-active compounds having theformula:

in which R represents a lipophile group that is a linear or branchedalkyl or alkenyl, which has 3 to 22 carbon atoms or an alkyl aryl groupwhich has 8 to 22 carbon atoms and has a linear or branched alkyl chainwhich has 1-! 8 carbon atoms, and in which n has a statistical averagevalue greater than I and less than l or equal to 10, essentiallycharacterized by the fact that :1 molecules of the glycerolepihalohydrin repeating group are linearly polyadded to a hydroxylatedcompound having the formula ROH, in which R has the significance indicated above, and that the resulting product is hydroxylated with acarboxylic acid salt.

A further object ofthe present invention is to provide the new articleof manufacture which consists of nonionic surface-active agentsaccording to formula I made by the foregoing process.

Another object of the present invention is to provide as new articles ofmanufacture, the intermediate products obtainted while carrying out theabovementioned process, after the polyaddition has taken place but before the hydroxylation, said intermediates having the formula:

in which R has the significance indicated above, it has a statisticalaverage value greater than 2 and less than ll) or equal to 10 and Xrepresents a halogen.

Broadly, the present application covers the class of non-ionicsurface-active agents described above and those which may be preparedfrom natural or synthetic aliphatic or alicyclic alcohols. The termnatural alcohols is intended to include those derived, for example. fromlanolin, natural waxes (e.g. beeswax), hydroabietic alcohols derivedfrom resinous acids, and alcohols obtained by reducing cyclic fattyacids. I

lt is known that lanolin alcohols, for example, comprise up to 30 carbonatoms, and that they consist of a mixture of straight or branched chainiso and anteiso derivatives, which are members of the aliphatic series,and of alicyclic alcohols (sterols and triterpenic alcohols). Thealcohols are found in lanolin, essentially in the form of esters offatty acids. Hydrogenation yields a mixture comprising both the alcoholsof the unsaponifiable material and those derived from the fatty acids oflanolin.

The preparation of lanolin alcohols by hydrogenation was described byStickdorn. E. Konig and Birk in the Tenside review, 3, No. 2 (1966) p.45.

Elrolan" sold by VEB Deutsches Hydrierwerk and Hydrolan R sold by OccoInternational, Division of Millmaster Onyx Corporation, Jersey City, NewJersey U.S.A. are examples of alcohols of lanolin prepared byhydrogenation.

High molecular weight alcohols may be obtained in like manner fromnatural waxes, (beeswax, for example) and from resinous acids.

It is another object of the present application to provide new non-ionicsurface-active agents having the formula:

in which n has a statistical average value greater than I and less thanID or equal to ID and R represents a hydrocarbon radical derived fromaliphatic or alicyclic alcohols, of either natural or synthetic origin,which may comprise from 8 to 30 carbon atoms and a process of makingthese compounds. This process is essentially characterized by the factthat n molecules of glycerol epihalohydrin are polycondensed on analcohol having the formula R OH, in which R, has the significancehereinbefore indicated, the resulting product is then hydroxylated bymeans of carboxylic acid salt, and the ester thus formed is hydrolizedor alcoholized.

it is a further object of the present invention to provide, as newcompositions of matter, the non-ionic surface-active agentscorresponding to formula (I) and (Ill) produced by the above process.

It is a still further object of the present invention to provide. as newcompositions of matter, the intermediates which are obtained in thecourse of the above process, after completion of the polycondensationstep and before hydroxylation, which intermediates correspond to thegeneral formula:

cpihalohydrin supplied per molecule ofalcohol. Consequently. the processaccording to the invention makes it possible to obtain a mixture ofcompounds having hydrophilic chains the size of which is dependent onthe value of the number n in formula W J. the group of values of n beingstatistically distributed about an average value corresponding to thenumber of molecules of glycerol epihalohydrin provided per molecule ofalcohol.

But the important point, which represents one of the essentialadvantages of the process according to the invention. is that it leadsto the formation of compounds having a single lipophile group for eachhydrophile chain.

Moreover, it should be pointed out that the process according to theinvention makes it possible to regulate the lipophile property oftheresulting product by varying the value of the number n of glycerolepihalohydrin molecules provided for each molecule of alcohol.

When n is at least equal to one-third of the number of carbon atoms inthe lipophile chain, the products are detergents which are soluble inwater. Moreover. the derivatives in which the lipophile chain containslO-l4 carbon atoms make good foaming agents, while those in which thelipophile chain contains more than 14 car bon atoms are emulsifiers.

When n is more than the condensation becomes difficult because beyondthis value, we obtain the phenomenon described in the JACS Vol. 82 Jan.60 No. 1 (Pages ll24) Latremouille, Merrall and Eastham, that is to say,the depolymerization of our products by formation of dioxane and ruptureof chain links.

in a preferred embodiment of the invention the glyc erol epihalohydrinis polycondensed in the presence of a Lewis acid catalyst such as borontrif'luoride, stannic chloride, or antimony pentachloride, at atemperature between and 160C.

When boron trifiuoride is used, this is introduced in the proportion ofl to 2 percent of the total reaction mass and the reaction is preferablycarried out at between so" and l20C.

The hydroxylation which constitutes the second step of the process makesit possible to avoid the disadvantages inherent in those reactions inwhich hydroxyl groups are directly substituted for halogens. it is wellknown that the preparation of hydroxylated compounds by hydrolysis ofhalogen derivatives is, in general, quite difficult. that thesubstitution is often incomplete, and that the presence of the mineralhalides has an adverse effect on the solubility and makes it labori ousto separate the desired end product. The hydroxylation step which ispreferred to use in the practice of the present invention consists inreacting the halogen derivative of formula (IV) with an alkaline salt ofcarhoxylic acid. preferably within a solvent which insures both themiscibility ofthe reagents and the easy separa tion of the halideformed. In this method. the selected solvents participate by progressivealcoholysis of the esters formed in an intermediate stage. Among thesolvents having the required properties are propylene glycol,dipropylene glycol. diethylene glycol, ethylene gly col, hexyleneglycol, 2-butoxy-ethanol. l,3-butanediol and ethers of diethyleneglycol, such as diethylene glycol monomethyl ether. diethylene glycolmonoethyl ether, diethylene glycol diethylether, diethylene glycolmonobutyl ether. diethylene glycol dibutyl ether, the boiling points ofwhich are sufficiently high to make it unnecessary to use an autoclave.in general. it has been found that the amount of solvent to be usedshould equal at least 50 percent by weight of the amount ofpolyhalogenated ether which is to be hydroxylated, and preferably from100 to 400 percent by weight.

The hydroxylation reaction is carried out at a temperature high enoughfor the speed of the reaction to be convenient and low enough so thatthere is no degradation of the products formed. A temperature between150 and 200C. and preferably between and lC is suitable. The percentageof hydroxylation resulting under these conditions is always greater than90 percent.

The alkaline salt of carboxylic acid used in the hydroxylation step isadvantageously an acetate in stoichiometric proportions or in slightexcess, (10 to l5 percent at the maximum) with respect to thehalogenated compounds participating in the reaction. it has been foundthat the results remain equally satisfactory when the acetates are addedall at once at the beginning of the hydroxylation step. or in successivefractions in the course of this reaction. [t is possible to regeneratethe acetates in situ from the esters formed during the reaction. forexample. by adding an aqueous solution of an alkaline hydroxide andinstantaneously evaporating the water.

Finally, in order to avoid coloring the products ob tained during thehydroxylation, it has been found that it suffices to add reducing agentssuch as sodium hypophosphite or alkaline borohydrides.

The products according to formula (Ill) are very valuable because oftheir emulsifying properties and their compatability with ionicsurface-active agents. This compatability makes it possible to introducethem into aqueous or hydroalcoholic solutions in association with ionicsurface-active agents.

It is a further object of the present invention to provide cosmeticcompositions, and particularly hair dye compositions, which areessentially characterized by the fact that they contain at least oneproduct corresponding to formula (Ill) or to formula (I) in amountsranging from I to 60 percent by weight of said composition and aconventional hair dye in amounts effective to color said hair.

These hair dye compositions may in addition contain other surface activeagents and/or carriers, thickening agents such as hydroxyethylcellulose,carboxymethyL cellulose etc.

It is another object of the present invention to provide an effectivepeptizing agent comprising said surface-active agents for dispersingsolid pulverulent material in non-aqueous liquid media, and particularlyin oils.

Still another object of the present application is to provide adispersion of solid pulverulent material in non-aqueous liquid media,and particularly in oils, said dispersion being characterized by thefact that it contains as a peptizing agent at least one compoundaccording to formula (lll). Preferably R in this formula (Ill)represents a radical derived from alcohols and sterols obtained byhydrogenation of lanolin. R may also represent a radical derived fromalcohols obtained by reduction of cyclic fatty acids.

A solid pulverulent material such as a pigment which is ground up in oilis frequently used in the cosmetic field. These pigments are oftenobtained by precipitation, and are dried. After drying theyre-agglomerate, so that they must be ground before being mixed with theoil. This grinding is not too fine because it is limited by themechanical means available. It has been suggested that the precipitatedproduct be dried in the presence of oil. However, experience has shownthat, even though insoluble in water, a large part of the pigment is notemulsified by the oil and re-agglomerates on drying. It has now beenfound that drying of such pigments in the presence of a peptizing agentaccording to the invention comprising a compound according to theformula (lll) redisperses the pigments in the oil while retaining theiroriginal degree of fineness. Representative oils employed include, forinstance, paraffin oil. vegetal oils, animal oils, modified animal oilssuch as perhydrosqualene or fatty acid esters such as isopropylmyristate.

Generally. the amount of oil employed ranges between about 50 to 99percent based on the total weight of the dispersion and the amount ofpeptizing agent can vary between about 1 to percent, based on the weightof the pulverulent material.

Moreover. it should be emphasized that the compounds of formula I in a 5percent aqueous solution are completely harmless and freely tolerated bythe mucous membrane of the eye. This property has been clearlyestablished by tests carried out on the eyes of a group of rabbits usingthe methods described by .l. H. Draize, G. Woodard and H. O. Calvery inthe Journal of Pharmacology" 1944, Vol. 82, pages 377-389 and by .l. H.Draize and E. A. Kelly in "Proceedings of Scientific Section, 17, 1-4,1952). No lesions of any nature appeared in the mucous membranes of theeyes of rabbits after such tests. Moreover, these compounds, whenassociated with cationic surface-active agents, cause no synergisticirritation. On the contrary, they decrease the irritation caused bycertain quaternary ammonium halides.

The cosmetic compositions according to the invention may be stocksolutions i.e. concentrates to be diluted before use and compositionsready for use.

The concentrates may contain up to 75 percent of the compounds offormulas l and Ill. The compositions ready for use are preferablyaqueous solutions comprising about 1-25 percent and advantageously 5-20percent of the compounds of formulas l and lll.

The above cosmetic compositions may contain other ionic or non-ionicsurface-active agents and the percentages indicated above include allthe surface-active agents.

Other conventional additives such as thickening agents may be added tothese compositions. When the hair is washed with these solutions itbecomes shiny, soft and non-electric.

It has moreover been found that the compounds according to formula I maybe used in cosmetic compositions as carriers for hair dyes. In general,such hair dye compositions have a pH of 3 to 9.

In order that the invention may be clearly illustrated. examples whichshow the general method of preparation and use of compounds of thisinvention will now be described.

EXAMPLE l Preparation of the compound C, H O+C H O(CH OH H in which nhas a statistical average value of about 4.

First steppolycondensation 186 g of lauryl alcohol and 1.5 ml of anacetic compound of boron fluoride containing 36 percent BF areintroduced into a flask adapted to hold a liter and provided withstirring means. a thermometer and a cooling coil.

The mixture is heated to C and 389 g of glycerol epichlorohydrin areadded drop by drop. The reaction is exothermic, and the temperaturestays between 75 and C. The operation lasts 75 minutes, after which thereaction mixture is permitted to return to room temperature.

The resulting polyoxychloropropylenated lauryl alcohol is a clear yellowoil which is insoluble in water. The epoxide function is measured toverify that the epichlorohydrin has completely reacted.

Second step-hydroxylation 144 g of potassium acetate are dissolved in360 g of dipropylene glycol. This solution is heated to C under anitrogen atmosphere.

181 g of the product obtained in the first step are added whilestirring. This takes 30 minutes. The mixture is then heated for 2% hoursat between 180 and C. After cooling it to room temperature, thepotassium chloride formed is separated by filtration. with a yield ofabout 96 percent of the quantity which should theoretically have beenformed.

The partially acetylated dipropylene glycol is evaporated under vacuumfrom the filtrate and a sirupy product soluble in water is thusisolated.

The index of saponiflcation determined for both the end product and therecovered solvent, shows that the polyhydroxylated polyether is 85percent deacetylated.

The product is then dissolved in 500 ml of absolute ethyl alcohol. Thissolution is colored with vegetable black and 300 mg of sodium ethylatedissolved in 10 ml of absolute ethyl alcohol are added. The resultingmixture is left at room temperature for 6 hours, which permitsde-acetylation of the product. After evaportion of the ethyl acetate andthe ethyl alcohol. 147 g of an end product having the followingcharacteristics are recovered:

Saponification index Hydroxyl index 546 lodine index 1 EXAMPLE 2Preparation of the compound having the formula 1-1 0 -[-C H O tCH OH) lH in which n has a statistical average value of about 4.

in a first step the glycerol epichlorohydrin is polycondensed on thelauryl alcohol in the manner described in Example 1.

1n the second step. hydroxylation is effected in the following manner:

0.84 mols of crystallized sodium acetate in the form of the trihydrateand 0.1 l g of sodium hypophosphite are dissolved in 115 g ofdiethyleneglycol. The solution is heated under a nitrogen atmosphere. When thetemperature reaches 120C the water begins to distill away. At l-l45Cgelification may be seen.

115 g of polyoxychloropropylene lauryl alcohol are then added within 20minutes. while stirring and maintaining the temperature between 140 and145C. The reaction mixture again becomes fluid. and is heated at 180C tocomplete the evaporation of the water.

The reaction is then continued at 180-185C for 3 hours. Under theseconditions from 95.5 to 96 percent of the sodium acetate involved isconsumed. After cooling to 80C. the solution is filtered and the sodiumchloride washed with 29 g of diethylene glycol at 80C.

The diethylene glycol is evaporated from the filtrate under vacuum andwhile heating to 180C. 107 g of a product having a saponification indexof 64 and 150 g of partially acetylated diethylene glycol having asaponification index of 244 are recovered.

The de-acetylation of the polyhydroxypolyether is terminated bysaponification with aqueous 13 percent sodium hydroxide at a temperatureof 40-45C. This step takes an hour and a half.

EXAMPLE 3 Preparatinn of the compound RO-LC H 0 (CH OH )hl'l (in which Rrepresents a linear aliphatic chain having 12 to 14 carbon atoms derivedfrom copra and n has a statistical average value of 4).

First step-polycondensation Proceeding as in Example 1. 370 g ofglycerol epichlorohydrin are reacted with 200 g of a mixture of fattyalcohols of copra consisting essentially of dodccanol and tetradecanolin the proportion of about 70 percent of the first to 30 percent of thesecond. This produces a polychlorinated polyether.

Second step-hydroxylation l 14 g of the compound thus obtained aredissolved in 200 g of dipropylene glycol. The solution is heated to 180Cand g of potassium acetate are added little by little. After 4 hours and30 minutes of reaction at 180C, 96 to 97 percent of the acetateintroduced has been consumed. The potassium chloride thus formed isseparated, the solvent is evaporated, and an indicated in Example 1, theproduct is dissolved in ethyl alcohol. The ethyl acetate and the ethylalcohol are then eliminated and 100.5 g of a sirupy product arerecovered. This product is soluble in water and corresponds to theformula given at the beginning of this example.

EXAMPLE 4 Preparation of the compound having the formula RO+C H 0 (CHOH)-],.H

(in which R represents a liner aliphatic chain having 12 to 14 carbonatoms. and n has a statistical average value of about 5.5.)

First step-polycondensation 1n the same way described in Example 1. 509g of glycerol epichlorohydrin are reacted with 194 g of a mixture offatty alcohols containing about 70 percent of dodecanol and 30 percentof tetradecanol in the presence of 1.5 m1 of an acetic compound of boronlluoride comprising 36 percent BF This yields a chlorinated polyetner.

Second step-hydroxylation 70 g of the polychlorinated polyether obtainedin the first step hereinbefore described are dissolved in 735 g of2-butoxy ethanol. The solution is heated to C. and 55 g of anhydrouspotassium acetate are then introduced little by little. over a period of40 minutes.

After reacting for 7 hours at 170C. the reaction mix ture is permittedto return to ambient temperature. 94 percent of the quantity ofpotassium chloride which should theoretically have been formed isseparated by filtration. After evaporation of the solvent 67.5 g of aproduct are recovered. which is then de-acetylated with ethanol. in thepresence of potassium hydroxide which acts as a catalyst. The ethylalcohol and ethyl acetate are then eliminated.

The resulting polyhydroxyl ether is soluble in water and is a goodfoaming detergent.

EXAMPLE 5 Preparation of the compound: RO+C H O (CH OHH- H (in which Ris an alkyl radical having 16 to 18 carbon atoms and n has a statisticalaverage value of 6.)

First step-polycondensation The method of operation is essentially thatof Example 1. 416 g of glycerol epichlorohydrin ae reacted at atemperature between 70 and 80C with 188 g of a mixture ofcetyl alcoholand stearyl alcohol in the presence of 0.87 percent of boron fluoride,yielding a polychlorinated polyether.

Second step-hydroxylation 156 g of the compound thus obtained are mixedwith 144.5 g of potassium acetate dissolved in hexylene glycol at atemperature between and C. The temperature is maintained for 3 hours.Then it is cooled to 25C and the potassium chloride formed is separatedby filtration. The hexylene glycol is then evaporated under a pressureof l-20 mm of mercury while progressively increasing the temperature to180C. The product is de-acetylated by ethanolysis with sodium ethylateas the catalyst. The ethyl acetate and the alcohol are eliminated, andl32 g of a pasty product which dissolves in water at 75C are recovered.

EXAMPLE 6 Preparation of the compound s MO+c H,o (CH OH -,,H

in which n has a statistical average value of 10.

First step-polycondensation In the same general way in Example 1, 462.5g of glycerol epichlorohydrin are reacted with 143.5 g of stearylalcohol in the presence of l l percent boron fluoride. The reactionmixture is kept for four hours at a temperature between 60 and 65C andthen heated to lC for 5 minutes. It is then stirred while beingpermitted to return to ambient temperature.

The result is a polychlorinated polyether.

Second step-hydroxylation 242.5g of the compound obtained in the firststep are heated with 200 g of potassium acetate, using 300 g ofdipropylene glycol as the solvent. The reaction is continued for 3 hoursat a temperature between 185 and 190C. The chloride ion and thepotassium acetate are then measured to determine the percentage oftransformation, which is found to be between 97 and 98 percent. Theresulting product is isolated and ethanolyzed as in Example I. After theethyl alcohol and ethyl acetate have been evaporated, the process yields177 g of a solid product which, in aqueous solution, is slightlyopalescent at C and limpid at 60C.

EXAMPLE 7 Preparation of the compound RO+C H O (CH OHH H (in which n hasstatistical average value of 5 and R is a branched chain alkyl radicalcontaining l l to l6 carbon atoms in the branch chain derived from analcohol obtained by 0x0 synthesis).

First step-polycondensation Using the method of Example l, 231.2 g ofglycerol epichlorohydrin are reacted with 105.5 g of a mixture of fattyalcohols obtained by Oxo synthesis, the branched hydrocarbon chain ofwhich contains 1 l to l6 carbon atoms. This reaction is carried out inthe presence of 0.75 ml of an acetic compound of boron fluoride.

This yields of polyoxychloropropylenated alcohol which is insoluble inwater and a deep brown in color.

Second step-hydroxylation 134.7 g of the compound thus obtained aredissolved in 876 g of dipropylene glycol, and l g of potassiumhorohydride is added to this solution. The mixture is heated whilestirring and loses color rapidly. 100 g of potassium acetate are thenadded. followed by 50 g of dipropylene glycol. After 3 hours of reactionat l75-l80C, 93.5% of the potassium acetate supplied has been consumed.

The potassium chloride is separated by filtration. after which thesolvent is evaporated by progressively raising the temperature to [Cunder a reduced pressure (15 to 20 mm of mercury). The resulting productis then subjected to ethanolysis in the presence of alcoholic potassiumhydroxide.

The ethyl acetate and alcohol are then eliminated and l35.5 g ofa sirupyliquid are recovered. This liquid dissolves easily in water and may beused as a foaming detergent.

EXAMPLE 8 First step-polycondensation Glycerol epichlorohydrin isreacted with commercial oleyl alcohol having a hydroxyl index of 207 andan iodine index of 88.

This yields polychlorinated mono-alkyl-ethers having the formula:

in which R designates the radical derived from the oleyl alcohol rawmaterial and n has the value 2, 4, 5 or 6. This reaction is carried outat about 60C. using, as a catalyst, an acetic compound of boron fluoridein the ratio of about 0.25 ml per I00 g of reaction mass.

Second stephydroxylation Value of n Appearance Solubility 2 Yellow oilDispersible in water 4 Yellowish paste Soluble in water with turbidity 5Clear brown paste Soluble in a hydroalcoholic medium containing 10%alcohol 6 Clear brown paste Soluble in water EXAMPLE 9 Firststep-polycondensation 343 g of Hexadecylic" alcohol, sold commerciallyby Esso, are reacted with I80 g of glycerol epichlorohy' drin in thepresence of 1.25 ml of an acetic compound of boron fluoride, yielding apolychlorinated ether having the formula:

ca-ca 0lc H 0 (cH c1H a 8 17 in which n has a statistical average ofl.5.

Second step-hydroxylation This polychlorinated ether is treated with aquantity of potassium acetate percent in excess ofthe stoichiometricquantity. After reacting for 5 hours at l80C, the resulting salt isfiltered and the dipropylene glycol which was used as solvent isevaporated off.

The crude product is then saponified with aqueous sodium hydroxide at 48percent by weight, washed in boiling water to eliminate theelectrolytes. and dried, to yield the hexadecylic monoether having theformula:

in which n has a statistical average value of [.5 and is an almostcolorless oil which is dispersible in water. The product canadvantageously replace the oleic de' rivative having the samehydrophilic chain. Because it contains no double bond, it does not turnrancid.

E XAM PLE First step-polycondensation 372 g of lauryl alcohol tie. theproduct sold under the trademark Alfol-lZ") are reacted at 8590C with278.5 g of glycerol epichlorohydrin in the prescnce of l.b5ml of anacetic compound of boron fluoride.

The result is a lauryl ether having the formula:

C H O+C H O tCH Cll-hH in which n has a statistical average value of1.5.

Second step-hydroxylation Third step-preparation of a sulfatedderivative 74 g of polyhydroxylated ether prepared in the first step aremixed with 6 g of urea and heated to 90C. 25 g of sulfamic acid are thenadded. The mixture is vigorously mixed using a turbo-mixer and heated onan oil bath to [20C. The reaction is then strongly exothermic and, whileheating is discontinued, the temperature rises to l40C.

The resulting sulfate dissolves readily in water and is a good foamingdetergent.

EXAMPLE ll Preparation of the compound in which n has a statisticalaverage value of about 6.

First step-polycondensation 2.5 ml of a phenolic boron fluoride compoundcontaining 26 percent BF are added to l67 grams of melted octylphenol. 4l 6 grams of glycerol epichlorohydrin are then added. drop by drop,while stirring. The reaction begins at 95C. after which the temperatureis lowered to 80C when the mixture will remain liq uid at the lattertemperature.

The epichlorohydrin is added over a period of 60 minutes. 0.5 ml of thephenolic boron fluoride compound is thcn added and the reactionterminated while continuing to stir the mixture.

No loss ot'weight due to evaporation of volatile products occurs whilethe mixture is being heated in a waterbath under a vacuum produced by awaterjet pump. The polychlorinated ether thus obtained is in the form ofa viscous oil.

Second step-hydroxylation 300 g of potassium acetate are dissolved in700 g of dipropyleneglycol and the resulting solution heated to 180Cunder a nitrogen atmosphere.

398 g of the product obtained in the first step are then added whilestirring the mixture of 170 minutes, after which it is heated for l00minutes at a temperature between l"C and l9()C. It is then cooled toroom temperature and the potassium chloride formed therein is filteredout.

The partially acetylated dipropylene glycol is evaporated under vacuumfrom the filtrate.

The product thus obtained is dissolved in 750 ml of absolute ethylalcohol; the solution is colored with vegetable black, and 30 ml ofalcoholic potassium hydroxide at half normal strength are added. Theresulting mixture is left at room temperature for 4 hours and 30minutes, thus de-acetylating the product. After evaporation of the ethylacetate and the alcohol 335 g of a product corresponding to the formulaat the beginning of this example are obtained in the form of a viscoussubstance which is soluble in water. This substance has good foamingpower and does not irritate the mucous membrane of the eye.

EXAMPLE 12 Preparation of the compound in which n has a statisticalaverage value of 6.

First step-polycondensation Following the method described in Example 1,416 g of glycerol epichlorohydrin are reacted with I72 g of commercialnonyl-phenol. A polychlorinated polyether is thus obtained.

Second step-hydroxylation 300 g of potassium acetate are dissolved in700 g of dipropylene glycol. The solution is heated to l80C. and 392 gof the product obtained in the first step are EXAMPLE l3 Preparation ofthe product represented by the formula RO-{-C H O(CH OH H- H in which Ris a hydrocarbon derived from lanolin alcohol obtained by catalytichydrogenation of lanolin and sold under the trademark EI.ROLAN by theVEB DEUTSCHES HY- DRIERWERK. and n has a statistical average value Firststep polycondensation 0.7 ml of an acetic complex of boron fluoride isadded to 103 g (25 percent of the molecularly equivalent amount ofalcohol) in the form of the above EL- ROLAN" which has been melted.

The mixture is heated to 7580C. and 92.5 g of glycerol epichlorohydrinare introduced, while stirring.

This addition is so regulated as to keep the temperature substantiallyconstant, as a result of the exothermic character of the reaction.

This operation takes 40 minutes. The reaction mixture is then heated ina water bath for 15 minutes.

The result is a polychlorinated ether in the form ofa viscous oil.

Second step-hydroxylation I566 g of polychlorinated ether are dissolvedin 160 g of dipropylene glycol. The mixture is heated to 145C. 260 g ofapercent aqueous solution of potassium acetate are then introduced. Inthe course of this operation the temperature is progressively increasedso as to eliminate water from the reaction mixture. This is thenmaintained at l80-l 85C. under a nitrogen atmosphere for 3 hours.

After cooling, the potassium chloride is separated by filtration. Theprecipitated salt is washed with hot dipropylene glycol. The solvent isevaporated from the filtrate at first under a reduced pressure of I5-20mm of mercury, and then udner a pressure of 1 mm.

The product is then introduced into 225 ml of absolute ethyl alcohol andsubjected to ethanolysis. For this purpose sodium methylate is used as acatalyst in the proportion of 0.275 g per I00 g of product to betreated.

The mixture is kept first at 35C so as to obtain a homogeneous mixture,and then left at room temperature overnight. After evaporation of theethyl acetate and ethyl alcohol. a yellow-brown paste is recovered whichcan be dispersed in water. The composition of this paste is representedby the formula given at the begin R0-l-C H O (ca ou mu in which n has astatistical average value of 7.6 and R represents the alkyl radical ofthe mixture of hydrogenated lanolin alcohols sold commercially under thetrademark ELROLAN".

First step-polycondensation of epichlorohydrin In this process 4l .3 gof the mixture of lanolin alcohols, 74 g of glycerol epichlorohydrin and0.4 ml of an acetic complex of boron fluoride are reacted together, theacetic complex of boron fluoride being introduced into the reactionmixture in three fractions:

0.2 ml at the beginning of the reaction;

0.] ml before the end of the addition of the first half of theepichlorohydrin used; and

0.1 ml while the second half of the epichlorohydrin is being introducedThe temperature is kept at 80-85C.

Under these conditions 93 percent of the epoxide introduced is consumed,i.e., 7.6 mols per molar equivalent of alcohol.

after evaporation of the glycerol epichlorohydrin the result is apolychlorinated ether represented by the formula:

in which R and 1| have the significance hereinbefore assigned thereto.

Second step-hydroxylation EXAMPLE l5 Preparation of the productrepresented by the formula RO-PC- H O (CH OHH; H

in which R represents the alkyl radical of the hydrogenated lanolinalcohols sold commercially under the trademark HYDROLAN" by OCCOINTERNA- TIONAL (DIVISION OF MILLMASTER ONYX CORPORATION). This rawmaterial has a hydroxyl 5 index of 154.

ning of the example. and it has the following character- 0 istics:

Hydroxyl index 372 Saponification index 9 The polycondensation ofepichlorohydrin and the hydroxylation reaction are carried out underconditions identical to those described in Example l3. The product thusobtained is in the form ofa soft water insoluble wax.

EXAMPLE 16 Preparation of the product represented by the formula RO-I-C-H O(CH OH H H in which R represents the alkyl of the lanolin alcoholssold under the trademark HYDROLAN".

The polycondensation of the epichlorohydrin is carried out at 8090C inthe presence of boron fluoride as a catalyst and in the proportion ofO.l percent of the total weight of the reaction mixture. Hydroxylationis brought about by heating at l80C for 4 hours and a half.

The polyhydroxyl polyether represented by the above formula takes theform of a yellow-brown paste.

It is dispersible in water.

EXAMPLE 17 Preparation ofthe product represented by the formula RO+C H O(CH OH H H an acetic complex of BF a polychlorinated ether is obtainedwhich responds to the formula:

+C H O (CH Clfl- H Second stephydroxylation 385 g of the polychlorinatedether obtained in the first step are dissolved in 580 g of propyleneglycol. The mixture is heated to 140C and 420 g of an aqueous 40.4percent solution of potassium acetate are introduced by progressivelyincreasing the temperature to 165C so as to eliminate the water from thereaction mixture.

After four and a half hours at l80l90C, the percentage of substitution.calculated from the acetate consumption, is 99 percent.

The potassium chloride is then separated and the di propylene glycolevaporated under vacuum. The diacetylation of the product is thenterminated by ethanolysis, using 0.25% sodium methylate as the catalyst.

After evaporation of the ethyl acetate and ethyl alcohol, a polyhydroxylpolyether is recovered in the form of a sirupy light yellow liquid.

This product is purified by washing it twice in boiling water, using oneliter of water in the first washing and l.5 liters in the second.

The products represented by the following formula are successivelyprepared in like manner.

n Appearance Solubility insoluble in water Soluble in vaselinc oilDispersihlc in water Soluble in vascline oil Soluble in water Insolublein vaseline oil 3 Very viscous liquid h Paste 9 Solid brown orangeAlthough the example set forth above can use R groups obtained byreacting commercially available fatty alcohol mixtures, similar resultsare obtained by using a single fatty alcohol, aliphatic alcohol oralicyclic alcohol. When a single or pure ROH reactant is used the Rportion of the compounds formed all have that R group.

The following alcohols further illustrate the type alcohols that can besubstituted in the above examples to produce the compounds of thisinvention which have the corresponding R and R groups present in thespecific alcohol reactant:

a. Saturated linear alcohols such as:

l-octanol l-decanol l-undecanol ldodecanol l-tridecanol l -tetradecanoll pentadecanol l-hexadecanol l-heptadecanol l-octadecanol l-eic osanol ldocosanol b. Unsaturated linear alcohols such as:

Oleyl alcohols (cis-9-octadecene-l-ol) Elaidyl alcohol(tranS-Q-octadecene-l-ol) Erucylic alcohol (cis-l3-docosene-l-ol)Branched chain alcohols such as:

Lethyl-l-hexanol Z-methyl-l-decanol Z-methyll -dodecanol2-methyll-tridecanol 2-methyl-l-tetradecanol 3,7, ll,lS-tetramethyl-l-hexadecanol 2, 3, 5, 7-tetramethyl-l-nonanol 2, 4,7-trimethyl-lnonanol 2-octyll -dodecanol Z-heXyI-l-decanolZ-methyl-alkanols d. Fatty alcohols derived from animal and vegetableoils and fats, such as: Copra Tallow, etc.

e. Mixed industrial alcohols such as those derived from the "ALFOIJprocess, the OXO" process, etc. These compositions contain a variety ofisomers and homologs which vary with the olefin feed that is beingconverted to the alcohol mixture.

1". Fatty alcohols prepared using the GUERBET reactron.

g. Fatty alcohols prepared using the method described in U.S. Pat.2,8l2,342.

h. Phenol alkyls, such as:

p-tert-octyl-phenol p-sec-octyl-phenol p-isononyl-phenolp-tert-dodecyl-phenol p-isododecyl-phenol and in general those alcoholswhich are obtained by alkylation of phenols with olefins such asdodecine, tripropylene, tetrapropylene and diisobutylene.

i. Aliphatic alcohols, such as:

ceryl alcohol melissyl alcohol cholesterol lanesterol ordihydrolanesterol mixtures obtained by catalytic hydrogenation oflanolin or resinic fatty acids.

The preparation oflanolin alcohols by hydrogenation was described by K.Stickdorn E. Konig and Birk in the TENSlDE review, 3, No. 2 (1966) p.45.

j. Saturated cyclic fatty alcohols such as:

CH -CH OH CH -CH (X y 10) Clu3(Cn2 5 (C3 )XCH2OH (K. r y

These cyclic alcohols have been described by Bellfriedrich Gast andCowan in JAOCS review, 42, October I965, on page 876.

Moreover. the compounds of the invention can be transformed by a knownprocess, into ionic surfaceactive agents by introducing ionic groupsinto the compound structure, such as sulfonate ions, carboxylate ions,phosphate ions, etc.

EXAMPLE l8 The following composition is prepared:

R(){-(. [H:( H2()H) '11 H in which R is an oleyl radical RO{-C,H,-.O(CHUH) 17 H in which R is an oleyl radical Z-butoxy ethanol 20% ammoniaEthylene diamine tetracetic acid Sodium bisulfite Paratoluylene diamineO Mctadiamino-anisol Resorcine 0.

Mcta-aminophenol Para-aminophenol Water, qsp.

MUQWWUOSGQUE COE F- This solution is mixed with an equal volume ofhydrogen peroxide at 20 volumes, thus producing a beautiful transparentgel. This gel is applied to very gray hair for 25 minutes. Aftershampooing, a chestnut shade results.

When dried, the hair is especially soft and lustrous.

EXAMPLE l9 The following composition is prepared:

in which R is an oleyl radical l Olein 6 50% dicetyldimethyl ammoniumchloride in isopropanol l2 Z-butoxy ethanol 10 Ethyl alcohol 8' ammoniaPnratoluylene diamine Resorcinc Meta-aminophcnol Para-aminophenol Methylpara-aminophenol Meta-diarninoanisol Ethylene diamine tctracetic acidSodium bisulfite Water. qsp.

uweueonuumcnuein ouuoaon mm a:

This solution is mixed with its own volume of hydrogen peroxide at 20volumes. When applied to very gray hair for 25 to 30 minutes, theresult, after shampooing, is a golden chestnut shade.

The hair, after treatment, is very soft and easy to manage.

EXAMPLE 20 The following composition is prepared:

Trimethylcetylammonium bromide Z-Butoxyethanol Ethyl alcohol 20% ammoniaEthylene diamine ten-acetic acid Paratoluylene diamine MctadiaminwanisolResorcine Metaaminophenol Para-aminophenol Sodium bisulfite Water qsp.

This solution is mixed with its own volume of hydrogen peroxide at 20volumes. When applied to very gray hair for 25 to 30 minutes, theresult, after shampooing, is a dark blond shade.

The hair. after treatment, is very soft and easy to manage.

EXAMPLE 20 A The same composition is prepared as in example 20 exceptthat cit-c11 0 [C2H30(CH2OH) l; 30 g is used instead of noC2H30(CH20H)}2 n 30 g R: olcyl The same good results are obtained as inexample 20.

EXAMPLE 2] The following composition is prepared:

This solution is mixed with its own volume of hydrogen peroxide at 20volumes. When applied to very gray hair for 25 to 30 minutes, theresult, after shampooing. is a fair blond shade.

The hair. after treatment, is very soft and easy to manage.

EXAMPLE 2] A The same composition is prepared as in example 21 exceptthat a us cn cn o- ['c n own omk H t. 5 8 t7 i usarrl instead of it:oleyl The same good results are obtained in example '1].

EXAMPLES 2] B 21 E The same composition is prepared as in example 21except that is replaced by the same weight of:

RO -[C H -,O(CH OH )-hH (EXAMPLE 2| B) in which R represents a linearaliphatic chain having 12 to l4 carbon atoms derived from copra.

in which R represents a linear aliphatic chain having 12 to l4 carbonatoms derived from copra.

in which R is a branched chain alkyl radical containing ll to 16 carbonatoms RO [-C H O(CH OH)-1T,H (EXAMPLE 2] E) in which R is a radicalderived from oleyl alcohol.

EXAMPLE 2?.

The following composition is prepared:

Ethyl alcohol 2U g 20% ammonia l 1 cm Ethylene-diamine tetracetic acid0.3 g Paratoluylene-diaminc 0.45 g Mcta-diaminoanisol 0.05 g s ResorcineU1 g Mcta-aminophenol (1.8 g Para-aminophenol 0.5 g Sodium bisulfite 0.6g Water q.s.p. I00 g [0 This solution is mixed with its own volume ofhydrogen peroxide at 20 volumes When applied to very gray hair for tominutes. the result. after shampooing. is a chestnut shade.

The hair. after treatment. is very soft and easy to H manage.

EXAMPLE 22 A The same composition is prepared as in example 22 exceptthat the two first components are replaced by R0 -[-C H O(CH OH )I H R=linear aliphatic chain having [2 to l4 carbon atoms 25 derived fromcopra and l l ,J

f -(H 0 C e n omn on) P a H a 30 V l J The same good results areobtained as in example 22.

EXAMPLE 22 B The same composition is prepared as in example 22 exceptthat the two first components are replaced by RC l-C H O(CH OH )-]-:H

R linear aliphatic chain having 12 to l4 carbon atoms derived from copraand R0 +C H OtCH OHfizH R= isostearyl The same good results are obtainedas in example 22.

l; X A M T Ll 23 Eur.

l ,B-hi s-y-amiiiupvopyl amino anihraqu inane IIIDOIQQDQQUIUII I S 1-dictlty1ami no ethylami11n2-nitro-h-Nfl-oiihydroxyethyl illllihO'lntnlfluntl ethydrochloride. a u c 0 u I a c e o a o n e e c o a 1 o l6 g l-N-mothyla|ii.lno--3-nitro-1--N-B-uminoetltylmniuo benzene O. 25 g[1-ltydroxy |-('y-mothylnwrplto] in i din) propy] amino anthtaqu'inonojmtliylsulfa 1.0. n .1 3'

2-B-am:i.noo Lhylzunino ant Iuuqitinoni: .(),2

1, i -d i B-aminopropy1ami no) anthraqtti nmi" f g EXAMPLE 23-Continued1-dimethylamino-B-aminocthylaininot-nitrobBDZGIIEIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIueve tjl1--methylmnino-4--amino-propylamino anthra uiuone. n L') c:

1-nmino-propylamino anthraquinonc...uu-n-uuu-nnu.. .i a:

1 ndiamino-S-aminopropylamino anthraquinone. .0. g

'j-niiro-h-B-aminoethylamino anisole monohydr-ochloride. .0.2 5

Carrier Laurie acid. u u I a r;

Diothanolamidn of c0pra.........................n..........1.00 g

Laury]. sodium sulfate oxyethylenated with 2 moles of ethylene Oxide. II I I I I I I I I I I I I I I II I II I II II I I I I I I I I I I I I III I I I a R-NH-CIHL-COONa on mom-(cu -N 3 2 2 J CH2V--CI1I3 CPL-CH &

I I I I I I I I I I I I I I I I I I I I I 1 I00 [5 R hydrocarbon radicalderived from fatty acids of copra n o-fc u omn om g-a. 5.00 g

R: nonylphanylUutylglyco]...H...........................................6. i;

w an lnmin ...........-.........-.....................0.6 G

Hydruxyethy] c llulose Fold hy Union Carbide and Carbon under the trademark "Cellosize W.P.3" {T CIISIPI I I I I I I I I I I I I II I I I I I II I I I I I I a I I I o I I I I I I I I I I I I100 g This composition isapplied for minutes to chestnut After shampooing a dark chestnut shadeis obtained hair containing percent to percent gray hair. masking thegray hair.

E X A M P L E 2 6 The following composition is prepared was 1 ,B-bis- 1'aminopropylamino anthraquinone. u -1 5 l;

I-diethylamino ethylamino-E-nitroh-KN d-ihydroxyethylamino benzenedihydrochlorideu-................-.H- .6 g

't-N-me thylamino-j-nitro -1 -N-B-aminoe thy) amino benzene .0 e 25 1-hydroxyt- (-y-me thylmorpholinium) propylamino anthraquinono 7m0thylsulfate. I I I I I I I I I I I I I I I I I I I I I I I I I I 0 gZ-B-aminoethylamino anthraquinone. .0.2 g

1, 5 di (B-an1inopropy1zunino) anthraqu-zinone. .0.3 g

1-dime thyl amino-S-amino e thylaminoh'nitro bellzene. I I I I I I I I II I I I I I I I II I II I I I I I I I I I I I I I I I I I I I I3 g I-nwthylmninob-amino propylamino anthraquinone -3 G 1-amino prcpylaminoanthraquinone. .0,15 g

1 4-diamino-5-y-aminopropylamino anthraquinoue. 4 g

3-411troh-B-aminoetlnylzunino unisole monohydrochloride .0,2

Lnuttlt: mild"InunI.u.n...H.nu.uunn-uu-J.

Divthunolrm-hie or copra-"nu".........-.-...........-.1. I

EXA MPLE 24C0ntinued Lanr'yl sodium sulfate oxyo thylennted wi th 2moles of othylenfi OXideI I I I I I I I I I I I I I I I I I I I I I I II I I I I I I I I I I I I I I I ISIOO R-NH-CH-COONB. cu -CH cu -corr-(cnN 2 3 1.00

I \CI!2-CH3 R hydrocarbon radical derived from fatty acids of" (opraR-O- [c rr o(cn 0ii):]-6-H.................................5.00

R octylphenylHutylglycol..................-................-......-...6.Monoethanolumineuu.....................=...............O.6

llydroxyt-thylccllulosc sold by Union Cmb isde and Carbon undvr thotrade mark "Colloeizv NJ. 3" .ISJJU wider 1. -1...........................-.............10

This composition is applied for minutes to chestnut gen peroxide at 20volumes. When applied to very gray hair containing 30 percent to 70percent gray hairv 30 hair for 25 to minutes, the result, aftershampooing,

E X A M P L E 25aminohydroquinone"........-.......nu...-.-.............0.

2,5 dihydroxy monomethylamino benzene. .0.7

G-hydroxy-S-me thyl-ZJt-diaminobenzcne. .1. 5

'4-hydr0xy-'J-amino-a.nisole hydrochloride- .1 .6

2, 5-diamino- &-methy1 phenol dihydrobromide. I I I 5 'i-XN-diethylamino-2,6-diaminopheno1 trichlorhydrate 6 diethanolamide Of copra. II I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I30 R NHH COONa Z 3 cu com; (CH2) N 3 CH -CH R a hydrocarbon derived from thefatty acids of copra C H o [C2H30 (CHOEQiFH..............-.--..........6.0

Sodium t 33' I I I I I I I I I I I I I I I I I I I I I I I I I I I I I II II I1.

NaOI-l 5N q.a.p. .......................p 7

Water qIBIpI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I II I I I III II II I I I After shampooing a dark chestnut shade isobtained is a brown shade.

H III R UK] N N N masking the gray hair. The hair, after treatment, isvery soft and easy to This solution is mixed with its own volume ofhydromanage.

3,865,542 25 26 EXAMPLE 26 C,- .H ,,O+[C H 0(CH OHJinH The samecomposition is prepared as in example 23 i no *1 exce [that i p IS usedinstead of diethunolumldc 0i cnpm- Hi0 g 5 The same good results areobtained as in Example 24.

EXAMPLE 28 Hm g The same composition is prepared as in cxzimplc 35 exisused instead of diethzmolamidc of copra i.()() g. Cept The same goodresults are obtained as in example 23. m CMHZSO+[CuHKNCHZOHHT5HliXAMPLlr 27 'l'hu sums cnmpusition is prepared as in uxalmplu 24 cxisused instead of diathanuiumidc of copru- 3.00 g. cup! that 35 The samegood rcsuits arc obtained as in example 25.

EXAMPLE 2! The T0 iuwim; cmiiipositicm in pruprn'vd Dzvs i, 8-1111!-ynmhmprupylnmino zmthrgiqujnonc. u c i i 1 if 1-413 0 Livy) amino rihyl:imj nil-11-nitr0- 1--T ;N-dil11,:ir0);ycthylwr'i i no iHHL'IlHdihydrochloridc [1-1iy(iruxy l--(' -mr!\hylmnr molin'ium) prom) aminozullhrnquLnoncjum lI-ylr-u] izite. l .1 .2

2-f3-zvminocthylwnino anthim njnonc r .0, 2 g

- r 1, 5-d1--( fi-uminopi'om'lzmii1m anthraqulnone 0,

1-me thjv'lamrrnol-amino-p1-0pylz1min0 unthraquinouc O. 3

1 1 .-d:izuiiino-fj-anxinupropyl;miino antliraquinonc u B-ni troi-B-ainiimc thylmnino anisolt: monohydrpr' hloride 2?.. 13-2:

Dicthunulwmidc 01 Coprru.H...................-...-...

Lnuryl sodium sulfate oxyotliylenuiied with 2 moles of (it-llYlCllCOXidC-nnunrno.oanoaoanooooooucooueooocu0o0onn05. f

R hydrocarbon radical (iv-rived from fatty acids of copra.

uht iinvd by (mt-11y iir ily il ur nriiion of ,irmn] in.

Buty1g1ycnl................................................6. E.

Monouthunolumiuo.....-...r.-..........................-...-. 1 i

Hydruxyvthylm)Julusc snhl by Union Carbide and Carbon under the trademark "Cullosizc NJ. 3" o -15 I:

Watcx' .s.p. ............H-.............-............"H1 (i 3,865,542 2728 This composition is applied for 20 minutes to Chestnut Thiscomposition is applied for 20 minutes to chestnut hair containing 30percent to 70 percent gray hair. hair containing 30 percent to 70percent gray hair EXAMPLE 3 The fol lowing; composition is prepared1,8--bisy-aminopropylamino anthraqninono. ,0,15 (3t-N-mrthylaminofl-nitwo-1-NBmn.in0uthy amino benzene O .25 g

/"1..1; ,'(l1-oxy-'t ('y-me thy1morpholinium) prnpylzuninoanthraquinonmethyl sulfate. J 5

2-B-n|ninoethy] amino zmthraquincme. r .0. 2

1,5 di (B-aminopropylamtno) anthraquinone .0 'j g1-djmothylwnrinn-j-uminn ethylmninot-nitrobenzcnenu......H...u...---................... .3 g

1-me thylaminrrt--uiuino propyl amino anthruquinone 0. 3 g

1-nnrino propylmnino anthruquinone. o 0.15 L! 1 h-rltiamino-5-y-aminopropylamino anthraquinone .0. 4 g

3-11itx'ot-B-mninoc thylnmino anisole monohydrochloride. .0.2 g

Laurie acid.........-.unu"..-...-.uunuunuu-ui. 0 (j! Diothunolamide ofcopraU..."u..uunuuuuun-nl. t3

Lnuryl sodium sulfate oxyethylenated wi t1] 2 moles of (ficthylene OXido-ucnone-acoovouaooan-cnooouoooculoouoculfic I:

R-NlL-Ctl-COONa t CIl -CH c:n -coz-t-(cn N 1100 g I .\c1r -cn R thydrocarbon radical derived from fatty acids of copra {c rr 0(cI-| on)}6 n V i, g R: octylphenyl rz-o fc n omn omjb 6 n 0. i g

H hylrocarbon radical derived from lanolin alcohols obtained bycatalytic hyrtr'ogvnatton of lanolin.

"Yhuxyuthylcc I lnloh'e :sold by Uni on Czizrbidu and CmbOn under thetrnricmark "(101105120 WA. 3 t .15- 1*.

watur 10S .1). a u c 0 a a 0 o n a I n 0 I a o 0 I 0 L n n o a 0 I 0 t 0o u o o n 0 Q o h n I t i 0 After shampooing a dark chestnut shade isobtained After shampooing a dark chestnut shade is obtained masking thegray hair. masking the gray hair.

E x A n P L E 31 aminohydr'o ulnone. u on one no. no .OJi g 2,5-dihyrlroxy monomethylamino benzene. 0.7 (I

6-hydroxy-'5mr thy12,h-diaminobenzene. .1 5 g--l.tydroxy--3-amlno-amisole hydrochloride. .1 .6 g

2 S-di amino-b-methyl phenol dihydrobr'omide. .0. g

h-NN-diethylmdnw-Z,6-diaminophenol trichlorhy lrate. .6 g

diethanolamide of copra. .3. g

n NI! cn COONa on -cn 2 on CONH (CH N R hydrocarbon derived from thefatty acids of copra c n o Ic n o (cn om g' n. 5. 5 g

R-0 Ec H o (Cfl Olflj-gn .0. 5 g

R: hydrocarbon radical derived from lanolin alcohols obtained bycatalytic hydrogenation of lan lin.

Sodium bisulfite 33 B. .icc

NH H 5N r m-1. .........pH 7

Wan-r .5.1 .....-........................-..............100 g Thissolution is mixed with its own volume of hydroglf ll a? 8-532 8 l1nelamine gen peroxide at volumes. When applied to very gray 40 f fii fjgjffl f 0004 5 hair for to minutes. the result. after shampooing, s diumsalt f thylene amine tetracetic L000 g 8C! shade- Sodium bisulfite d=1.32 1.200 g The hair, after treatment, is very soft and easy to Waterq.s.p. I00 g manage.

30 of that com osition are mixed with h dro en er- EXAMPLE 32 P y g Pmode at 20 volumes. The following composition is prepared: A smoothdense cream is obtained which is pleasant to use.

When applied to 100 percent gray hair for 30 min- Cetyl-stearyl alcohol20 g h I f olcyl diehanohmide 4 8 utes t e resu t a ter shampoomg andrinsing IS a pleasg H,,O{-C H O(CH,OH)1 H 6 g ant blond shade. The halrafter treatment IS very soft yes zmdiaminmaniso sulfate on s and easy tomanage, the hair IS shiny, silky and pleasant Resorcine 0.420 g t0lOUCh.

The following composition is prepared 2 1 B--b;| .'--y-uminopropylmninonnthrnqninone Q 5 L;

i--l-.'-mo thylmnino -B-nLtro-J -N-[i-aminoothylmuino benzene .0. 25

[ 1-11ydxo7xY-l-(y-nu: thylmorphol in ium) propylnmino mithruquinoimjmcthylsulfnte. a .0.1 g

EXAMPLE 34-(ontinued Laurieacid.............-.-.........-......unnuuuul. l.

Lauryl sodium sulfate oxyethylmmted with 2 moles of Methyleneoxidc...............---...................UuS- (I l V on mos-(cu CH -CHN 2 3 C ll 3 R hydrocarbon radical derived from fatty acids of copra.

no fc n own omj z-n It: hydrocarbon radical derived from alcoholsobtained by the atalytic l'iytlrogcnafiion of' commercial acid.

ir os tearic y fl ycol. a n o c I I a o o u n a n o c o a a I 0 l o a ue 0 o 0 l o o I I t O I I I I l no (Tlanriuc........................................-0. r;

"Y mCyethylcellulosc, sold by Union Carbide and Carbon under the trademark "Collosize NJ. 3"

will-0r q-s-p.

This composition is applied for 20 minutes to chestnut hair containingpercent to 70 percent gray hair. Aftcr shampooing a dark chestnut shadeis obtained masking the gray hair.

EXAMPLE Peptization of barium sulfate Barium sulfate is precipitated bypouring a 2.4 N solution of barium chloride into a 1.6 N solution ofsodium sulfate. at the boil, and while stirring. The precipitate iswashed by simple decantation. It is very fine and few of its particleshave a dimension greater than 4 u.

5 percent of the following product is added to the barium sulfate Inthis formula R represents a hydrocarbon derived from the alcoholsobtained by hydrogenation of the lanolin sold under the trademarkElrolan". The other compounds in which n= 2. 3 and 7.6 may also be used.

The product is carefully dried and is found to be perfectly wetted byoil so that it may be introduced into emulsions The example of bariumsulfate is given purely by way of illustration. Other pigments such astitanium oxide, iron oxide, and Guimet blue may also be peptized.

EXAMPLE 36 Composition for use as lip rouge This example illustrates theuse of the product:

a n 0 u I o n o u n u o 1 a 0 o e Q Q i t 0 o o u u u 0 n 0 u o 0 n c no I I t I for peptizing metallic particles it) g of Bentone 38(trademark of National Lead Co.) which is an organophilic bentonite (acationic colloidal earth) are dispersed in a liquid consisting of 88 gof paraffin oil and 2 g of the product in which R has the samesignificance as in Example 35, and excellent homogenization is producedby vigorous stirring. The dispersion thus obtained is dispersed in theremaining components of a lip rouge, and l to 15 percent of flakes ofaluminium paint are introduced into the mixture. which is kept more orless liquid.

What is claimed is:

l. A composition for dyeing hair comprising an aqueous solution of ahair dye in amounts sufficient to color said hair and a compound havingthe formula CH OH ca cH-0 H wherein R, is selected from the groupconsisting of alkyl having 8-22 carbon atoms, alkenyl having 822 carbonatoms. alkyl aryl having 8-22 carbon atoms wherein the alkyl moiety hasl-l8 carbon atoms and the hydrocarbon radical derived from lanolinalcohols obtained by the catalytic hydrogenation of lanolin. n has astatistical average value greater than 1 and equal to or less than 10,said compound being present in O UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3r865I542 Dated Februar 11, 1975 Q Inventor(s)Gregoire Kalopissis and Guy Vanlerberghe It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

9 In the Heading Please add the following [30] Foreign ApplicationPriority Data April 23, 1965 Luxembourg 48458 Nov. 22, 1965 Luxembourg49902 April 6, 1966 Luxembourg 50850 a Dec. 1, 1967 France 130713 Signedand gealecl this ninth Day Of September 1975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Q Allesling Officer (mull-mm, 'Pamm andTrademarks F ORM PO-1050 (IO-69) USCOMM-DC 60376-F-63

1. A COMPOSITION FOR DYEING HAIR COMPRISING AN AQUEOUS SOLUTION OF AHAIR DYE IN AMOUNTS SUFFICIENT TO COLOR SAID HAIR AND A COMPOUND HAVINGTHE FROMULA
 2. A composition for dyeing hair comprising an aqueoussolution of a hair dye in amounts sufficient to color said hair and atleast one compound of the formula
 3. The composition of claim 2 whereinR1 is alkenyl.
 4. The composition of claim 2 wherein R1 is alkylaryl. 5.The composition of claim 2 wherein R1 is the hydrocarbon radical derivedfrom lanolin alcohols obtained by the catalytic hydrogenation oflanolin.
 6. The composition of claim 2 wherein R1 is alkyl.
 7. A methodof dyeing hair comprising applying to said hair the composition of claim2 in amounts effective to dye said hair.